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For intrinsic semiconductors, they don't have any free electrons at conduction band at 0k and behave like insulators. But if doped, let's say n-type doped, they will have extra electrons which do not have chemical bond to restrict them.

Will these doped semiconductors behave like metal conductors, or even "superconductors" at 0K?

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Dopants in a semiconductor require a small thermal energy to ionize. Without this energy, an electron donor atom will just keep its electron, and an acceptor atom will keep its hole. So at 0 K, a semiconductor will be an insulator, doped or not.

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